Polyvinyl butyral compositions



Patented May 15, 1945 s 2.370.030 YOLYVINYL BUTYRAL COMPOSITIONS La Verne E. Cheyney, Akron, hio,-.aolignor to Wingioot Corporation, Akron, Ohio, a corporation of Delaware No Drawing. than. April" 21, 1943, Serial' No. 483,923

' 1 Claim.

butyral compositions. More particularly, it relates to such compositions which are highly resistant to the passage of gases, such as hydrogen, oxygen, nitrogen. etc. 3

In general, the addition of a plasticizer to a plastic material softens the material and decreases its resistance to the passagev of gases.

It is exceptional when the addition of a plasticizer increases the resistance of ,a plasticto the passage of gases. In fact, those plasticizers which do not greatly reduce the gas resistance oi'plastics are finding wide application; for example, in the production of collapsible life-saving rafts, pontoons, aviators suits, etc.

According to this invention, polyvinyl butyral, which maybe one of the commercial grades of material which includes some of the nonhydrolyzed ester,v is plasticized with -a material of 'the, class consisting of a mixture of methyl,

phthalyl ethyl glycollate and amorphous wax (the mixture produces greater resistance to the passage of gas than the addition of either alone would indicate); 2-amino-2-ethyl 1,3 propane-diol; methylene dimorpholine (prepared by the interaction of morpholine and formaldehyde) 2,2 .-di- 4-morpholinyl diethyl amine (prepared by the interaction of diethylene tri'amine and 13.3- dichloroethyl ether as described in Hardman'U. S. 2,328,976) p-benzyloxy propionitrile (which may be prepared according to the process of Australian Patent 116,260) a-methyl-d-phenyl g l y c e r y l ether; di-isopropyl glyceryl ether; and an ethanol I amine. such as phenyl ethanolamine, and ethyl phenyl ethanolamine. The invention is applicable to each of the present commercial types of polyvinyl butyral which difier somewhat .in composition; viz., Butvar (Monsanto Chemical Company), Vinylite X (Carbide and Carbon Chemical Company), and Butacite (E. I. du Pont degNemours and Company).

It is known that methyl phthalyl ethyl glycollate is highly compatible withpolyvinyl butyral (Kocher U. S. 2,184,426). It is known that the plasticized composition containing an amorphous wax has a relatively high resistance to the pas unplasticized composition.

sage of gases. Compositions containing up toparts or more (per of resin) of methyl phthalyl ethyl'glycollate were practically as resistant to. the passage of hydrogen gas as the unplasticized material. This resistance was markedly increased by the additionof up to 25 parts of various waxes, such as paraflin, Santowax, or amorphous petroleum waxes. The crystalline waxes,

parts SS wax or This invention relates to plasticized polyvinyl however, tend to stiffen the compositions when used in more thantrace'amounts. The preferred composition is, therefore, a combination of the resin and methyl phthalyl ethyl glycollate an amorphous wax, especially the amorphous petroleum wax known as S8 wax, sold by the National Wax Company. The composition may, for example, be composed of 100 parts polyvinyl butyral, 30 parts methyl phthalyl ethyl glycollate, and 5 parts, methyl phthalyl ethyljglycollate, and 5 parts SS wax. The composition may also contain other materials, such as stabilizers, pigments, colors, etc. The wax-containing composition possesses an additional advantage over the nonwax one; namely, markedly improved resistance to the effects of water. The composition can be immersed in or exposed to water for relatively long periods 109 parts polyvinylbutyral, 50

of time with little harmful effect. This is not true of the wax-freecomposition;

Compositions containing the wax without the methyl phthalyl ethylglycollate have high resistance to the passage of gases, but it does not follow that all combinations of plasticizer and amorphous wax are excellent. The amorphouswax was tested in combination with many other plasticizers, including those of this invention, with out beneficial effect; the combination withmethylphthalyl ethyl glycollate is'unique in the benefits obtained. The wax alone (without the methyl phthalyl' ethyl glycollate) does not produce a composition of sufficient flexibility. The amorphous waxes are believed to be mixtures, consisting-of very high boiling, high molecular weight hydrocarbons, chiefly isoparamnic in nature, but probably containing some cyclic material. They may contain a small amount of crystalline waxy material in admixture. V

2-amino-2-ethyl-1,3-propane-diol is a good plasticizer for polyvinyl butyral, and the plasticized composition has a high resistance to the passage of gases. containing 30 parts 2-amino-2-ethyl-1,3 -propanediol:100 parts resin gave a rate of diflusion of hydrogen gas considerably less than that of an Methylene dimorpholine (prepared by the interaction pf m'orpholine and formaldehyde) and 2,2'-di-4-morpholinyl diethyl amine (prepared by the interaction of diethylenetriamine and -fi.fi'-dichloroethyl ether) have both been found to be good plasticizers for polyvinyl benzyloxy propionitrile, these morpholine com- For instance, a composition 2 poundsiormalro m."which compounded pobvinylbutyralgiveplastic'swhichhavesuperior flexibility at low temperatures. Although theirrate orgasdimisionmaybesomewhat mane:- than that or other materials here mentioned, they have a relatively hlsh resistance to the passage or gases. Examples of compositions possessing these desirable properties are: 100 resin+25 methylene dimorpholine 100 resin+25 ar-di-i-morpholinyl (llittliylasraoa'o with I 100 resin+55 2,2'-di-4-morpholinyl diethyl l00resln+25 p'-benzy1oxypropionitrile 100 resin +45 p'-benzyloxy propionitrile 0f the glyceryl ethers, di-propyl glyceryl ether is especially valuable as a plasticizer tor polyvinyl butyral because the plasticized composition has high flexibility at low temperatures and, likewise, has-high resistance tothe passage of gases. a-methyl-e' phenyl glyceryl ether,

- likewise, oilers great resistance togasdiflusion and, in addition, is highhr compatible with the polyvinyl butyral.

sitions are; J r

100 resin+25 di-isopropyl glycerol ether 100 resin+35 ,di-isopropyl glyceryl ether 100 resin-+25 methylphenyl glyceryl ether 100 resin-l-io metl'iyl phenyl glyceryl ether Compounds which are good plasticizersfor polyvinyl butyral and yield a plasticiaed product having high gas resistance include. the ,phenyl ethanolamines, which may be represen ted'by the formula: I

R.Ph.l lH(CaH4.OH) y .in-which Ph' isphenyl, n is hydrogen or alkyl;

ris 0 or 1, u is l or 2, and the sum or a: and z! is 2. Stress-strain data obtained on films 0.002- 0.005 inch thick are given in the following table, from which it will be noted that the general eflect of plasticizers 01 this class is todecrea'se the ultimate tensile strength and the load of the plastic at any "given elongation while the ultimate elongation is increased: r

Examples of these compostres -mm properties of plasticized film Other beneficial eii'ects, such as increased flexibility, resistance to shock, cutting action or tearing action, are, likewise, Produced by these plasticizers. Theeffect oi the plasticizer is, of course, within limits, proportional to the amount of the particular plasticizer employed and varies with the diil'erent members or the general class; Othen'example's 01. this 'general class might include. methyl phenyl di-J- ethanolamine, butyl phenyl diethanolamine, etc. The phenyl ethanolamine and; ethyl 'phenyl ethanolamine, as well as the other members of the general .class' mentioned above including. those included in the general formula for this class, form compositions which are highly re- I sistant to the passageof ga'sesg'lfheiormer is flexible at low temperatures. 'I'he'latter has high resistance to water. Examples of such compositions are those listed above and others containing even larger amounts of the plasticizers.v A composition which gave an extremely low rate of difiusion of hydrogen gas contained 35 parts 01 ethyl phenyl ethanolamine and 100- oi resin. This composition was as resistant to thegas as a mixture of'methyl phthalyl ethyl LA mm srossrmrr.

glycollate and wax,; mentioned above The examples listed are intended to be only illustrative and do not limit the compositions. The compositions'may' be in any 01' the forms known in the art. (such as molded. products, calendered sheet material, castfllm, textile or paper coatings, etc.

Whatliclaimis:

A composition composed essentially of polyvinyl butyral and 2,2'-di-4-morpholiny1 diethyl amine as a-plasticlzer. I i v cssrrrrosrs 0F connscrrom It ishereby cer'ti'ried 'that error appears in the printed spec-1f1cation f o f the above numbered patent 'reguir'ing correction, follows: lage 1, first co1umn,'1i.ne i+5, beforaknowh". insert not-; pageZ, first column, line for- "di-p'ropyl." ant should be read with this to the record. of the casein fiscal) read --d1i.sopr'op ylcorrection therein that the Patent Office-' signed 'and sealed/this 21st day or August, A.- D. 1915..

andthat the said Letters 'P atthe same may conform f a Leslie Fraz e-r 2 poundsiormalro m."which compounded pobvinylbutyralgiveplastic'swhichhavesuperlor flexibility at low temperatures. Although theirrate orgasdimisionmaybesomewhat mane:- than that or other materials here mentioned, they have a relatively hi h to the passage of gases. Examples of compositions these desirable properties are: 100 resin+25 methylene dimorpholine 100 resin+25 gr-di-bmorpholinyl (llittliylas'raoa'o with I 100 resin+55 2,2'-di-4-morpholinyl diethyl l00resln+25 p'-benzy1oxy propionitrile 100 resln+45 p'-benzyloxy propionitrile 0f the glyceryl ethers, di-propyl glyceryl ether is especially valuable as a plasticizer tor polyvinyl butyral because the plasticized composition has high flexibility at low temperatures and, likewise, has-high resistance tothe p of gases. c-methyl-e' phenyl glyceryl ethr,

- likewise, oilers great resistance togasdiflusion and,- in addition, is highhr compatible with the polyvinyl butyral. Examples of these compositionsarez 100 resin+25 di-isopropyl glycerol ether 100 resin+35 ,di-isopropyl glyceryl ether v 100 resin-+25 methylphenyl glyceryl ether 100 resin-i-io metl'lyl phenyl glyceryl ether Compounds which are good plasticizersfor polyvinyl butyral and yield a plasticiaed product having high gas resistance include. the ,phenyl ethanolamines, which may be repres'eri teil'by the formula: I

R.Ph.l lH(CaH4.OH) y .in-which Ph' isphenyl, n is hydrogen or alkyl;

ris 0 or 1, u is lorihand the sum 0! a: and z! is 2. Stress-strain data obtained on films 0.002- 0.005 inch thick are given in the following table, from which it will be noted that the general eflect of plasticizers 01 this class is todecrea'se the ultimate tensile strength and the load of the plastic at any "given elongation while the ultimate elongation is increased: r

stres -mm properties of plasticized film Other beneficial eii'ects, such as increased flexibility. resistance to shock, cutting action or tearing action, are, likewise, Produced by these' plasticizers. Theeffect oi the plasticizer is, of course, within limits, proportional to the amount of the particular plasticizer employed and varies with the diil'erent members of the general class; Othen'example's 01. this 'general class might include. methyl phenyl di-J- ethanolamine, butyl phenyl diethanolamine, etc. The phenyl ethanolamine and; ethyl 'phenyl ethanolamine; as well as the other members of the general .class' mentioned above including. those included in the general formula for this class, form compositions which are highly re- I sistant to the passageoi ga'sesg'lfheiormer is flexible at low temperatures. 'I'he'latter has high resistance to water. Examples of such compositions are those listed above and others containing even larger amounts of the plasticizers.v A composition which gave an extremely low rate of difiusion of hydrogen gas contained 35 parts 01 ethyl phenyl ethanolamine and 100- oi resin. This composition was as resistant to thegas as a mixture of'methyl phthalyl ethyl cssrrsrcm's LA mm glycollate and wax,; mentioned above The examples listed are intended to be only illustrative and do not limit the compositions. The compositions'may' be in any 01' the forms known in the art. "such as molded. products, calendered sheet material, castfllm, textile or paper coatings, etc.

Whatliclaimis:

A composition composed essentially of polyvinyl butyral and 2,2'-di-4-morpholiny1 diethyl amine as a-plasticlzer. I t v 0? connscrrom 1 l5: 9 4-5 s. cm.

It ishereby cer'ti'ried 'that error appear-s in the printed spec-1f1cation or the above numbered patent'reouiring column, line 1+5, befora' known'l insert for- "di-p'ropyl." ant should be me with this to the record. of the casein read --d1i.sopr'op ylcorrection thereinthat the Patent orricet' signed 'and sealed/this 21st day or August, A.- D. 1915..

conr'ect'ionja 1011's": lage. l, firstf not-; pageZ, first column, line an dthnt the said Letters 'Patthe same may conform f a Leslie Fraz e-r 

